Polymerization catalyst and process



United, States Patent 3,129,211 PGLYMERHZATEON CATALYST AND PROCESS Gordon D. Brindeli and Alian J. Lundeen, Ponca City, Okla, assignors to Continental Oil Company, Ponca City, Okla, a corporation of Deiaware No Drawing. Filed Nov. 5, 1959, Ser. No. 851,022 4 Claims. (Cl. 260-94.9)

This invention relates to novel catalyst and process for the preparation of low density, high molecular weight tion of David W. Marshall, Serial No. 851,019, filed November 5, 1959, and now abandoned. This invention relates to new and improved organometal-transition metal halide catalyst and method for the preparation of the polymers of Serial No. 851,019.

It is an object of this invention to provide improved catalyst and process for the polymerization of ethylene.

It is another object of this invention to provide improved catalyst and process of the polymerization of ethylene to polymers of low density and high molecular weight.

Still another object of this invention is to provide improved catalyst comprising an organometal compound and transition metal halide for the polymerization of ethylene.

These and other objects of the invention will become more readily apparent from the following detailed description and discussion.

.The foregoing objects are realized broadly by providing a catalyst composition comprising an organometal compound and a transition metal halide, present in a ratio of at least about 30 moles of organometal compound per mole of transition metal halide.

In one aspect of the invention the catalyst comprises a hydrocarbon soluble metal halide.

The catalysts of the present invention comprise generally the conventional transition metal halide polymerization catalysts. It is well known in the art that the various transition metal halides, for example, chlorides, bromides, etc., of the metals of groups III, IV, V, VI, VII and VIII of the periodic table are active in the polymerization of ethylenically unsaturated polymerizable monomers, and particularly low molecular weight mono-olefins such as ethylene. The halides of the metals of groups lV-A, V-A and VI-A are especially active in polymerization, particularly the halides of titanium, zirconium, vanadium, chromium, and molybdenum. A very eflzective catalyst and the preferred one of this invention is titanium tetrachloride.

A wide variety of organometal compounds can be em ployed in combination with the transition metal halide. These compounds include alkyl, cycloalkyl, aryl and alkaryl derivatives of various metals particularly alkali metals of groups I-A of the periodic table and metals of groups II-A, II-B and III-A, IV-B, V-B, etc., including titanium, aluminum, beryllium, zinc, indium, gallium, magnesium, boron, etc. Particularly useful organometals are the alkali metal alkyl compounds and alkali metal alkaryl compounds, which include specifically materials such as amyl sodium, parasodio tertiary butyl benzene, phenyl sodium, etc.

3,l29,2i 1 Patented Apr. 14, 1964 Specific examples of catalyst systems which can be employed in this invention include titanium tetrachloride and triethyl aluminum, amyl sodium and titanium tetrachloride, phenyl sodium and zirconium tetrachloride, zinc diethyl and titanium tetrachloride, phenyl lithium and titanium tetrachloride, and the like.

Generally the polymerization reaction is carried out in the presence of a liquid diluent which serves as a carrier for the catalyst, as a heat sink for polymerization temperature control and as a diluent for the polymer product. The diluent, which is usually a hydrocarbon can be any material ordinarily employed in polymerization catalyst systems comprising an organometal compound and a transition metal halide. Specific diluents include parafiins such as butane, pentane, hexane, heptane, etc., cycloparafiins such as cyclohexane, cyclopentane, methyl cyclopentane, and the like. Usually the diluent is selected from compounds containing from about 6 to about 12 carbon atoms. 1

The polymerization reaction conditions, forexample, temperature, pressure, time, etc., employed in the polymerization reaction vary depending on the composition of the polymerization catalyst. In general the reaction conditions correspond to those which are well known in the art and can be varied as required for the particular polymerization system. For convenience low temperatures in the order of 50 to C. are ordinarily employed, however, more elevated temperatures up to as high as 200 C. can be used if desired. The reaction pressure is not critical and usually is determined only by the limitations of the equipment employed. The reaction time can also vary widely and is established primarily by the degree of conversion desired.

Various methods of combining the catalyst components can be employed however, generally the catalyst is prepared by suspending or dissolving the organometal compound in a hydrocarbon diluent such as previously described. Thereafter the metal halide, for example, ti tanium tetrachloride is added to the admixture of organometal compound and diluent. The ratio of catalyst components in the catalyst system can be varied substantially, however, an excess of the organometal compound is necessary to provide a mole ratio of said compound to metal halide of at least about 30:1 and up to as high as 400:1. Although higher ratios than 400:1 can be used, in practice it is desirable to keep the ratio relatively low since the amount of polymer formed in the polymerization reaction is proportional to the amount of titanium present in the catalyst.

While, in general, any of the metal halide polymerization catalyst can be employed in the catalyst composition of the invention, preferably the hydrocarbon soluble halides are used since these halides provide a catalyst sys-' tem in which improved contacts is obtained between the catalyst components.

The polymers which are prepared from the catalyst of this invention are characterized by their extreme linearity, relatively low unannealed density (0928-0935 at 23 C.) and extremely high molecular weight (over one million). They have very high tensile strength and are substantially insoluble in hydrocarbon solvents, both aliphatic and aromatic.

The following examples are presented in illustration of the invention:

EXAMPLE 1 chloride, the components of the catalyst mixture being present in different amounts in different runs. The reactor was heated to 75 C. and pressured to p.s.i.g.

with ethylene. In each run the reaction time was two reason thereof and that many variations and modifications hours and at the end of this time the contents of the are within the scope of the invention. reactor were emptied into methanol to decompose residual We claim: catalyst. The polymer was then dried in a vacuum oven 1. A composition consisting essentially of an organoand tested to determine its various properties. sodium compound and titanium tetrachloride characterized A control run was also carried out in the same reactor in that the mole ratio of organo-sodium to titanium tetrawith the following differences in procedure, (1) 2.5 liters chloride is from about :1 to about 400: 1. of dry normal hexane, (2) 100 C. reaction temperature, 2. A composition consisting essentially of amyl sodium (3) 400 p.s.i.g. reaction pressure. and titanium tetrachloride, characterized in that the mole The properties of the polymers obtained in the various 10 ratio of amyl sodium to titanium tetrachloride is from runs are set forth in Table I. about 3021 to about 400:1.

Table I Reac- Ethyl- Initial Elonga- RNa, TiOh, NaR tion ene Reae- Yield, Per- Denmelting Remelt Tensile tion, Solubility Branches,

Run No. moles moles TiOh tempprestion g cent sity at point, point, strength, perin tetralin, 1,000 carerature, sure, time, ash 2 23 0. 0. 0. p.s.i. cent 7 130 (J. bons 0. p.s.i.g. hrs.

H I-117 (Control) 0. 47 0. 2 2. 100 400 2 131 0. 99 0. 949 124-130 4, 235 480 Soluble 1- HH Iii-115 0. 1 0005 200 75 150 2 21 0.71 0.935 199-200 125-13 Insoluble 0. 1 00025 400 25 150 2 21 0. 67 0. 932 191-198 127-133 d 0. 1 001 100 75 150 2 107 0. 19 0. 931 190-193 127-134 6, 810 0. 1 001 100 25 150 2 115 0. 50 0. 929 190-193 127-133 7, 150 0. 1 002 50 150 2 302 0. 27 0. 933 189-192 128-134 6, 250 HH II-121 0. 1 002 50 25 150 2 300 0. l1 0. 928 186-189 128-135 7, 045

1 Mixed alkyl sodiums (oetyl and amyl). gMmriulapgly-mer is heated in a mufizie iurnaee at 575 C. until the inorganic ash attains constant weight.

4 The granular polymer is observed through a microscope equipped with a hot stage using polarized light. The initial melting point or better, initial melting range, is the temperature Where birefringence oi the particles starts to disappear and where it has completely disappeared.

5 The apparatus is the same as above. After the initial melting, the polymer is allowed to cool and crystallize. The remelt range is the beginning and end of disappearance of birefringence.

6 AS'IM D638-58-T 20 min. crosshead speed.

7 ASTM D638-58T.

8 This was actually to be a molecular weight determination by ASTM D-1601-58T using tetrahydronuphthalene. The polymers all proved insoluble and molecular weights could not be run.

9 An infrared method, see W. D. M. Bryant and R. 0. Voter, I. Am. Chem. 500., 75, 6113 (1953).

10 Molecular weight (number average) was 525,000.

11 Insuflleient sample for test.

Norn.1he polymers prepared with the catalyst of this invention are characterized by their extreme linearity and relatively low density. They also have lower elongation and substantially greater tensile strength than the polymer of the control run.

EXAMPLE 2 Two runs were carried out in a one quart low pressure reactor in which the reactor was charged with 500 milliliters of dry normal hexane and a catalyst mixture composed of aluminum triethyl and titanium tetrachloride.

3. A process for the preparation of low density, high molecular weight polyethylene which comprises contacting ethylene under polymerization conditions with a catalyst consisting essentially of an organo-sodium com- The molar ratio of catalyst components differed in each pound and titanium tetrachloride Fhaljacterized in h run The reactor was Pressured to 40 psig. ethylene the mole ratio of organo-sodium to titanium tetrachloride pressure to produce polymerization. At the end of the 13 from about 30:1 to about40051- polymerization period, the catalyst was decomposed with A Process for the Preparation of low density, high methanol and the polymer was washed with a solution molecular Weight P y y Which Comprises of hydrogen chloride in methanol to remove residue tacting ethylihe Under Polymerization conditions with a catalyst. The polymer product had some solubility in catalyst consisting essentially of amyl sodium and Tetralin at 130 C. but the solution was too viscous to titanium tetrachloride, characterized in that the mole ratio measure molecular weight. A control run Was 8180 arof amyl sodium to titanium tetrachloride is from abti'ut ried out under the same reaction conditions. 30:1 t bo t 400:1,

Properties of the polymer product are given in Table II.

Table II AlEta, T1614, Tem- Ethylene Percent, Density, Tensile Percent Run No. moles moles AlEta/TiCli perature, Pressure, Yield, g. Ash 1 23 C. 1 Strength, Elonga- C. p.s.i.g. p.s.1. 3 tion DWM III-71 .014 .00028 50 25 40 41 0.07 0.930 5,835 250 DWM III-72 .014 .00014 100 25 40 22 0.11 0.931 5, 510 200 DWM III-96 0.021 0.007 3 25 40 39 0.955 4, 080 480 (Control).

1 Same as in Example 1. I Same as in Example 1. 3 Same as in Example 1. 4 Same as in Example 1.

In this series of runs, as in Example 1, the catalyst of R f r s Cited in the file of this patent the invention produces a polymer having substantially UNITED STATES PATENTS different properties from the product obtained with the 2 867,612 Pi et 1 6, 1959 conventional catalyst. 2,886,561 Reynolds et a1. May 12, 1959 Having thus described the invention by providing 2,924,594 Breslow 1960 specific examples thereof, it is to be understood that no FOREIGN PATENTS undue limitations or restrictions are to be drawn by 75 533,362 Belgium May 16, 1955 

3. A PROCESS FOR THE PREPARATION OF LOW DENSITY, HIGH MOLECULAR WEIGHT POLYETHYLENE WHICH COMPRISES CONTACTING ETHYLENE UNDER POLYMERIZATION CONDITIONS WITH A CATALYST CONSISTING ESSENTIALLY OF AN ORGANO-SODIUM COMPOUND AND A TITANIUM TETRACHLORIDE CHARACTERIZED IN THAT THE MOLE RATIO OF ORGANO-SODIUM TO TITANIUM TETRACHLORIDE IS FROM ABOUT 30:1 TO ABOUT 400:1. 